JP2008031195A - Fluorine-containing elastomer for lamination of adhesive-coated metal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing elastomer for lamination of adhesive-coated metal in which interlayer adhesiveness to metal enabling direct lamination to metal is improved. <P>SOLUTION: The fluorine-containing elastomer for lamination of adhesive-coated metal is composed of a fluorine-containing monoolefin/fluorine-containing diene copolymer elastomer having a peroxide-crosslinkable group or amine-vulcanizable group. The fluorine-containing elastomer is directly bonded to an adhesive-coated metal and a fluorine-containing elastomer layer is subjected to crosslinking with a peroxide or vulcanization with an amine to form a fluorine-containing elastomer-laminated metal. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a fluorine-containing elastomer for adhesive-coated metal lamination. More specifically, the present invention relates to a fluorine-containing elastomer for laminating an adhesive-coated metal with improved interlayer adhesion to metal.

  Conventionally, fluororubber has been used as a molding material for various seal parts used in high-temperature environments. However, due to the high performance of automobile engines, seal parts that can withstand use in higher-temperature environments are required. It is becoming. In addition, although fluororubber is excellent in heat resistance and oil resistance, it is inferior in resistance to organic solvents such as ethers and ketones, so that application to parts for sealing them is hindered. It cannot be used for rolls for alkali or organic solvent cleaning processes, copiers, printer rolls, and the like.

  In order to compensate for the disadvantages of fluororubbers, perfluoroelastomers have been used instead, but this is often used for O-rings that form sealing parts. In fact, parts that are combined with metals such as seals and rolls are rarely used because their bonding methods have not been established. Also, vulcanized adhesives for perfluoroelastomers are not commercially available.

In response to this situation, an organic peroxide cross-linked perfluoroelastomer layer is laminated via a vulcanized adhesive layer mainly composed of a silane coupling agent formed on a metal and an organic peroxide cross-linked fluororubber layer. Perfluoroelastomer laminated metal obtained by the above has been proposed. However, since it is necessary to form an organic peroxide cross-linked fluororubber layer between the adhesive layer and the perfluoroelastomer layer, there is a problem that the manufacturing process is complicated and the cost is increased.
JP 2000-272045 A

Also, in order to improve the adhesion between the fluorine-containing elastomer and metal, the surface of the vulcanized fluorine-containing elastomer is chemically treated such as sodium / ammonia method or sodium / naphthalene / tetrahydrofuran method or physical treatment such as leather or plasma treatment. However, there is a problem that the former requires a special working environment from the viewpoint of safety, and the latter requires an expensive device.
Adhesion technology Vol. 25, No. 4, p. 51 (2006)

  An object of the present invention is to provide an adhesive-coated metal-containing fluorine-containing elastomer with improved interlayer adhesion to metal, which can be directly laminated to metal.

  The object of the present invention is achieved by a fluorine-containing elastomer for laminating an adhesive-coated metal comprising a fluorine-containing monoolefin / fluorine-containing diene copolymer elastomer having a peroxide crosslinkable group or an amine vulcanizable group. When such a fluorine-containing elastomer is directly bonded to an adhesive-coated metal and the fluorine-containing elastomer layer is peroxide-crosslinked or amine vulcanized, a fluorine-containing elastomer laminated metal is formed.

  Since the fluorine-containing elastomer for laminating an adhesive-coated metal of the present invention can be firmly laminated directly onto a metal plate by using a commercially available adhesive, the fluorine-containing elastomer is bonded onto the metal plate. In this case, there is an excellent effect that the formation of a fluororubber layer between the adhesive layer and the fluorine-containing elastomer layer and the chemical and physical treatment of the surface of the fluorine-containing elastomer are not required.

  As the metal on which the fluorine-containing elastomer is laminated, soft steel, stainless steel, aluminum, aluminum die-casting, etc. are used, and the shape varies depending on the type of product. It is a rod-like body.

  On these metals, an adhesive, for example, a vulcanized adhesive mainly composed of a silane coupling agent, is applied, dried at room temperature, generally air-dried, and preferably further at about 120-200 ° C. for about 5-10. Bake for about a minute. As the silane coupling agent, commercially available vulcanized adhesives mainly composed of at least one of aminosilane and vinylsilane, such as Rhode products Chemlock AP-133, Y4310, 607, etc., can be used as they are.

On the vulcanized adhesive, an unvulcanized fluorine-containing elastomer is bonded as a composition. The fluorine-containing elastomer comprises at least one fluorine-containing monoolefin such as vinylidene fluoride, hexafluoropropene, tetrafluoroethylene, perfluorovinyl ether, chlorotrifluoroethylene and a fluorine-containing diene compound in the presence of a crosslinking point forming compound. It is obtained by polymerization, and ethylene, propylene and the like can be further copolymerized there. Here, examples of the perfluorovinyl ether include the following compounds.
CF ₂ = CFOCF ₃
CF ₂ = CFOC ₂ F ₅
CF ₂ = CFOC ₃ F ₇
CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] _{1 to 4} CF ₃
CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] _1-4 C ₃ F ₇
CF ₂ = CFO (CF ₂ ) _n OCF ₃
CF ₂ = CFOCF ₂ CF ₂ O (CF ₂ O) _n CF ₃

  More specifically, copolymers of vinylidene fluoride and other fluorine-containing monoolefins, such as vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene terpolymer, vinylidene fluoride / hexaflupropylene copolymer Examples thereof include tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymers and the like.

  In the fluorine-containing elastomer, the fluorine-containing diene compound is copolymerized at a copolymerization ratio of 0.001 to 1 mol%, preferably 0.1 to 0.5 mol% in the copolymer. If the copolymerization ratio is less than this, the effect of improving the adhesiveness intended by the present invention will not be observed, while if the copolymerization ratio is higher than this, the processability will deteriorate and the polymer cost will also increase.

As the fluorine-containing diene compound, at least one kind of fluorine-containing diene having 4 to 8 carbon atoms as described in Patent Document 2 below, for example, CF ₂ = CF-, CF ₂ = CH- or CF ₂ = CFO- With one terminal unsaturated group, specifically CF ₂ = CFCF = CF ₂ , CF ₂ = CF (CF ₂ ) ₄ CF = CF ₂ , CF ₂ = CFCH = CF ₂ , CF ₂ = CHCH = CF ₂ , CF ₂ = CF (CF ₂ ) ₂ CF = CF ₂ , CF ₂ = CFO (CF ₂ ) ₂ OCF = CF ₂ , CF ₂ = CFO (CF ₂ ) ₂ OCF ₂ CF (CF ₃ ) OCF = CF ₂ , CF ₂ = CFO (CF ₂ ) ₂ OCF (CF ₃ ) CF ₂ OCF = CF _{2 and the} like.
JP-A-55-108410

In the fluorine-containing elastomer, an amine vulcanizable group composed of a bromine-containing group, an iodine-containing group and a peroxide-crosslinking group or a cyano group which is at least one of bromine-iodine groups is also introduced. Examples of the peroxide crosslinkable group or amine vulcanizable group include the following saturated or unsaturated bromine-containing compounds, iodine-containing compounds, bromine and iodine-containing compounds, or cyano group-containing compounds.
CF ₂ = CFBr
CF ₂ = CFI
CF ₂ = CHBr
CF ₂ = CHI
CH ₂ = CHCF ₂ CF ₂ Br
CH ₂ = CHCF ₂ CF ₂ I
CF ₂ = CFOCF ₂ CF ₂ Br
CF ₂ = CFOCF ₂ CF ₂ I
CH ₂ = CHBr
CH ₂ = CHI
Br (CF ₂ ) ₄ Br
I (CF ₂ ) ₄ I
Br (CH ₂ ) ₂ (CF ₂ ) ₄ (CH ₂ ) ₂ Br
I (CH ₂ ) ₂ (CF ₂ ) ₄ (CH ₂ ) ₂ I
ICF ₂ CF ₂ Br
CF ₂ = CFO (CF ₂ ) _n OC (CF ₃ ) FCN
CF ₂ = CFO (CF ₂ ) _n CN
CF ₂ = CFO (CF ₂ C (CF ₃ ) FO) _m (CF ₂ ) _n CN

  A fluorine-containing elastomer having a peroxide crosslinkable group obtained by copolymerizing a fluorine-containing diene compound is crosslinked by an organic peroxide. Examples of the organic peroxide used as the crosslinking agent include tertiary butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydro Peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, di-tertiary butyl peroxide, dicumyl peroxide, tertiary butyl cumyl peroxide, 1,1-di (tertiary butyl peroxy) Cyclododecane, 2,2-di (tert-butylperoxy) octane, 1,1-di (tert-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di ( Benzoylperoxy) Sun, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (tert-butylperoxy) valerate, benzoyl peroxide, m-toluylper Oxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tertiary butyl peroxyisobutyrate, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxybenzoate, tertiary butyl Peroxyisopropyl carbonate, tertiary butyl peroxyallyl carbonate, and the like are used at a ratio of about 0.1 to 10 parts by weight, preferably about 0.5 to 3 parts by weight, per 100 parts by weight of the fluorine-containing elastomer.

  When performing peroxide crosslinking, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, triallyl trimellitate, trimethylolpropane trimethacrylate which are multifunctional unsaturated compound co-crosslinking agents Ethylene glycol dimethacrylate and the like are preferably used at a ratio of about 1 to 10 parts by weight, preferably about 2 to 5 parts by weight, per 100 parts by weight of the fluorine-containing elastomer.

R：炭素数1〜6のアルキリデン基またはアルキレン基、炭素数1〜10のパーフルオロ アルキリデン基またはパーフルオロアルキレン基、SO₂基、O基、CO基、２つのベ ンゼン環を直接結合させる炭素−炭素結合
X：水酸基またはアミノ基

n：1〜10の整数

R₂：H、NH₂
n：1〜10の整数
好ましくは、

R₃：H、OH
R₄：H、NH₂
好ましくは、

In addition, the fluorine-containing elastomer having an amine vulcanizable group obtained by copolymerizing a fluorine-containing diene compound is vulcanized by the amine compound. As the amine compound used as a vulcanizing agent, any of the amine compounds represented by the following general formulas [I] to [IV] is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight per 100 parts by weight of the fluorine-containing elastomer. It is used in the ratio.

R: C 1 -C 6 alkylidene group or alkylene group, C 1 -C 10 perfluoroalkylidene group or perfluoroalkylene group, SO ₂ group, O group, CO group, carbon directly bonding two benzene rings -Carbon bond
X: Hydroxyl group or amino group

n: Integer from 1 to 10

R ₂ : H, NH ₂
n: an integer from 1 to 10, preferably

R ₃ : H, OH
R ₄ : H, NH ₂
Preferably,

  In the composition comprising each of the above components, other compounding agents such as reinforcing agents, fillers, acid acceptors, anti-aging agents, lubricants, plasticizers, pigments, and the like are further added as necessary. After being kneaded with a closed kneader or the like, it is bonded onto a metal plate on which an adhesive layer has been formed. For peroxide crosslinking, about 180 to 200 ° C. for about 2 to 10 minutes, and for amine vulcanization, about 190 to 220. Laminated and integrated by pressure crosslinking or pressure vulcanization performed at about 10 to about 20 minutes to form a fluorine-containing elastomer laminated metal.

  Next, the present invention will be described with reference to examples.

Example 1
In an autoclave with an internal volume of 3 L, 1300 ml of deionized water, 2.2 g of 1-bromo-2-iodoperfluoroethane, 18.2 g of ammonium perfluorooctanoate, 1.5 g of disodium hydrogen phosphate dodecahydrate, fluorine-containing diene Compound [DVE3PO] 5 g, perfluoro (methyl vinyl ether) [FMVE] 45 g and tetrafluoroethylene [TFE] 42 g, while maintaining the temperature at 50 ° C., 1.5 g ammonium persulfate dissolved in deionized water and 0.03 sodium bisulfite 0.03 g was charged with a press-fitting device to start the reaction. A TFE / FMVE (molar ratio 65/35) mixed gas was added for 8 hours so that the pressure was maintained in the range of 1.0 to 0.9 MPa. After completion of the reaction, 5% potassium alum solution was added to the resulting aqueous emulsion to coagulate the resulting polymer, filtered, washed with water and dried to give 490 g of a rubbery polymer (measured by F-NMR). Polymer composition: TFE / FMVE / DVE3PO = molar ratio 65 / 34.9 / 0.1).
DVE3PO: CF ₂ = CFO (CF ₂ ) ₂ OCF (CF ₃ ) CF ₂ OCF = CF ₂

  100 parts by weight of the obtained polymer, 20 parts by weight of MT carbon black, 3 parts by weight of hydrotalcite (Kyowa Chemical Product DHT-4A), 2.2 parts by weight of triallyl isocyanurate (Nippon Kasei Chemical) and 2,5-dimethyl-2 , 5-Di (tertiary butyl peroxy) hexane 2 parts by weight (NIPPON OIL & PRODUCTS PERHEXA 25B-40; 40% purity) kneaded with 1L kneader (Moriyama product) and open roll, resulting kneading The product (fluorinated elastomer composition) was press-cured at 180 ° C for 10 minutes and oven-cured (secondary crosslinking) at 200 ° C for 6 hours to create a sheet-shaped test piece, which was hard (conforms to JIS K6253) ), Strength at break, elongation at break (based on JIS K6251), and compression set (based on JIS K6262) were measured.

  In addition, a solution prepared by dissolving 4 times the amount of methylethylketone, an adhesive mainly composed of aminosilane and vinylsilane (Lord Co., Ltd. Chemlock AP-133), was applied to the surface of zinc phosphate treated steel plate (SPCC) for 30 minutes at room temperature. After drying, baking was performed at 150 ° C. for 30 minutes. An uncrosslinked fabric made of the fluorine-containing elastomer composition as described above was bonded onto the adhesive layer-formed metal plate, and pressure-crosslinked at 180 ° C. for 6 minutes to produce a fluorine-containing elastomer laminated metal plate. Using the obtained fluorine-containing elastomer laminated metal plate, a 90 ° peel test was performed in accordance with JIS K6256.

Comparative Example 1
In Example 1, the fluorine-containing diene compound [DVE3PO] was not used in the copolymerization reaction. Using the obtained polymer (498 g), measurement of physical properties and 90 ° peel test were conducted in the same manner.

Example 2
In an autoclave with an internal volume of 3 L, 1300 ml of deionized water, 20 g of perfluoro (2-cyano-3,7-dioxa-8-nonene), 18.2 g of ammonium perfluorooctanoate, disodium hydrogen phosphate, 12 hydrate 1.5 g, DVE3PO 5 g, perfluoro (methyl vinyl ether) [FMVE] 45 g and tetrafluoroethylene [TFE] 42 g were charged, while maintaining the temperature at 50 ° C., 1.5 g of ammonium persulfate dissolved in deionized water and sodium hydrogen sulfite 0.03 g was charged with a press-fitting device to start the reaction. A TFE / FMVE (molar ratio 65/35) mixed gas was added for 12 hours so that the pressure was maintained in the range of 1.0 to 0.9 MPa. After completion of the reaction, 5% potassium alum solution is added to the resulting aqueous emulsion to coagulate the resulting polymer, filtered, washed with water and dried to give 500 g of a rubbery polymer (measured by F-NMR). Polymer composition: TFE / FMVE / DVE3PO = molar ratio 67 / 32.9 / 0.1).

  Each component of 20 parts by weight of MT carbon black and 1.4 parts by weight of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane per 100 parts by weight of the obtained polymer was added to a 1 L kneader (Molyama product) and an open roll. The kneaded product (fluorinated elastomer composition) obtained by kneading at 220 ° C., press vulcanized for 15 minutes and further in a nitrogen atmosphere, (1) held at 90 ° C. for 4 hours, (2) 90 ° C. to 204 ° C. (3) Hold at 18 ° C for 18 hours, (4) Increase from 204 ° C to 288 ° C over 6 hours, (5) Oven vulcanize under conditions of 18 hours at 288 ° C (Secondary vulcanization) was performed to prepare a sheet-like test piece, and the physical property values were measured in the same manner as in Example 1. In addition, an uncrosslinked fabric made of the fluorine-containing elastomer composition as described above was bonded onto the adhesive layer-forming metal plate produced in the same manner as in Example 1, and subjected to pressure vulcanization at 200 ° C. for 10 minutes. A fluoroelastomer laminated metal plate was produced, and the obtained fluorine-containing elastomer laminated metal plate was subjected to a 90 ° peel test in accordance with JIS K6256.

Comparative Example 2
In Example 2, the fluorine-containing diene compound [DVE3PO] was not used in the copolymerization reaction. Using the obtained polymer (498 g), measurement of physical properties and 90 ° peel test were conducted in the same manner.

The results obtained in the above examples and comparative examples are shown in the following table.
table
Measurement Item Example 1 Comparative Example 1 Example 2 Comparative Example 2
Normal physical properties Hardness (Duro-A) 81 80 75 80
Strength at break (MPa) 18.5 18.2 17.9 18.0
Elongation at break (%) 150 170 240 170
Compression set (%) 23 20 28 27
90 ° peel test peel strength (N / mm) 2.9 0.3 3.2 0.5

Claims (6)

  A fluorine-containing elastomer for laminating an adhesive-coated metal comprising a fluorine-containing monoolefin / fluorine-containing diene copolymer elastomer having a peroxide crosslinkable group or an amine vulcanizable group.   The fluorine-containing elastomer for adhesive-coated metal lamination according to claim 1, comprising a copolymer elastomer in which the peroxide crosslinkable group is a bromine-containing group, an iodine-containing group or a bromine-iodine group.   The fluorine-containing elastomer for metal-coated adhesives according to claim 1, comprising a copolymer elastomer in which the amine vulcanizable group is a cyano group.   The fluorine-containing elastomer for adhesive-coated metal lamination according to claim 1, wherein the fluorine-containing diene compound is a copolymer elastomer which is a fluorine-containing diene compound having 4 to 8 carbon atoms.   The fluorine-containing elastomer for laminating an adhesive-coated metal according to claim 1 or 4, comprising a copolymer elastomer obtained by copolymerizing 0.001 to 1 mol% of a fluorine-containing diene compound. A fluorine-containing elastomer laminated metal obtained by directly bonding the fluorine-containing elastomer according to any one of claims 1 to 5 to an adhesive-coated metal and subjecting the fluorine-containing elastomer layer to peroxide crosslinking or amine vulcanization.